Carboxylic acid-polyamine reaction mixture



o sneeze Patented Aug. 21, 1962 Stars Parent In carrying out the invention, the liquid acids are first 3,050,529 charged to a mixing vessel and then the sebacic acid is CARBUXYLIC ggg jft REACTION stirred in. Agitation is continued throughout the reaction period. The acid mixture is deoxygenated at a pressure g gfi zggg g 3222 2 g gg i' 32 5 of about 15 mm. Hg, the vacuum is released with nitrogen (Iiiribrifih, Mass; at cfirporation of Cimnecticut nd a blanketiug stream of nitrogen is thereafter used No Drawing. Filed g 23 1950 Sen N 73,374 throughout the reaction. Following deoxygenation, the

3 Claims. (Cl. 260-3096) acids are heated to about 70 C., the requisite amount of triethylene tetramine is added and the temperature rises This invention relates to compositions containing a toabout100 C, d t lt f ti complex compound having a plurality of imidazoline rings Immediately after adding all of the triethylene tetraas a principal constituent. In another aspect it relates mine, the system is protected during synthesis against to a method for preparing such compositions by contactcatalytic pro-oxidant metals by the addition of a chelating ing a plurality of diverse carboxylic acids and a polyand inactivating agent. These metals, which are introethylene polyamine under reactive conditions. duced as impurities in the acid and amine reactants, cat

Monoimidazolines, such as undecylirnidazoline, and alyze degradation of the reaction product with a consediimidazolines, such as octamethylene diimidazoline, are quent increase in viscosity and darkening of the product. known but have limited utility. The complex polyimid- Even small leaks in the packing surrounding the agitator azoline of this invention has a high molecular weight, is shaft through which atmospheric oxygen can gain entrance strongly basic, and possesses strong surface activity. When into the mixing vessel can cause a tenfold increase in the incorporated with a polymeric material, such as polymers viscosity. The agent is added in amounts sufiicient to and copolymers of vinyl chloride, it performs admirably react with substantially all of the metallic impurities as a curing agent. present in the reactants and generally between about 0.1 The present compositions are prepared by heating at percent to 0.5 percent by weight based on the total weight reduced pressures under nitrogen and with vigorous agitaof the acids and amine has been found satisfactory. Suittion a mixture comprising triethylene tetramine, oleic acid, able agents include the alkali metal polypliosphates, such sebacic acid and a mixture of polymerized acids conas sodium and potassium tripolyphosphate. sisting of about 75 percent di'rneric and 25 percent tri- The mixture is then heated at 1 atmosphere to about meric acids derived from a mixture of unsaturated 18- 150 C. at which point the pressure and temperature are carbon monocarboxylic fatty acids. (The mixture of adjusted periodically in inverse relationship according to polymerized acids is a product supplied commercially by the following schedule:

Emery Industries, inc, under the trademark Empol Imidazoline formation Proceeds essentially in Heating period in minutes after Temperature, Pressure, two steps. In the first step, a terminal amino group of reaction mixture has reached mm. s the polyamine reacts with a carboxyl group to form an at amide with the release of one mole of water. Then, a

. 152.5 580 second mole of water splits out from the amide group 1525 435 and a secondary amino group beta to it, causing cyclization 155 335 165 235 to give an imidazoline. Dicarboxylic acids reacting with 1825 135 polyamines in this manner produce a complex polyimid- &2 azoline containing imidazoline rings plus some amide 51 35 groups and secondary amino groups resulting from in 220 15 complete cyclization. The reaction yields a mixture comprising a major amount f (1) a pglyimidazoline having Since water catalyzes side reactions and hydrolyzes imidthe following idealized structure: azolines, it is removed as it is formed in order to achieve 1% mole (sebacic acid residue) H and I-lzNCH1-CHzl CHiCH2NCl-4 mole (dimeric-trimeri0- I ll acid residue) i ii I Inc N 2 CH2 CH2 GET-(CH2)7-CH=CI*I-(CH2)7-C-lTTCH2-CH QT CH2 in which up to about 15 percent of the original carboxyl maximum conversion to imidazoline. The above schedule group are i th f f u t d id permits removal of water as fast as possible consistent with imidazoline conversion without distilling appreciable [I 1 amounts of tetramine. During the reaction period, the G-NCH2 CH2 agitator should be run at a high rate of speed to give derived from the reaction of acid with primary amine a high surface turnover of the mixture for rapid water groups, and/or N-substituted amides removal. An agitator speed of about 100-200 rpm. 0 R has been found to be satisfactory. Experiments have g l shown that low water removal caused by decreasing the derived from either hydrolysis of previously formed speed from about 150 to 65 rpm. lowered the imidazoline imidazoline rings or the reaction of acid with Secondary content by about 10 percent due to irreversible hydrolysis amine groups, and/or (2) species of imidazolines and of the imidalolil'le Tingpolyimidazolines having higher and lower molecular After a mp r r of about 220 C. and a pressure weights than the molecular weight of the idealized polyof about 15 mm. Hg have been reached within three imidazoline structure. hours according to the foregoing schedule, this pressure and temperature are held and the reaction mixture is heated for about one hour under these conditions. Thereafter the product is cooled to 150 C. under nitrogen and collected. The viscosity of the reaction product averages about 1200 centipoises at 60 C. The average composition as determined by infrared absorption analysis is comprised of structures resulting from about 85 percent conversion of the carboxyl groups to imidazoline rings with the remaining 15 percent of the carboxyl groups existing as amide groups.

The molar quantities of acids and amine used to prepare the reaction mixture are 3 moles of sebacic acid, 4 moles of oleic acid, 1 mole of Empol 1024 and 8 moles of triethylene tetramine.

The invention is further illustrated by the following examples:

Example 1 67.7 lbs. (.24 mole) of oleic acid and 36 lbs. (.06 mole) of Empol 1024 were mixed together in a glass vacuum vessel and then 36.4 lbs. (.18 mole) of sebacic acid were added. The acids were heated to about 70 C. and then 70.2 lbs. (.48 mole) of triethylene tetramine were added. Due to the exothermic reaction of amine and acids, the temperature of the mixture rose to about 100 C. 0.21 lb. of powdered sodium tripolyphosphate was then added as a metal chelating agent. Vigorous agitation and a nitrogen atmosphere Were maintained throughout. The mixture was then heated at 1 atmosphere to about 150 C. and the temperature and pressure were carefully controlled thereafter for a fourhour period according to the pressure-temperature schedule set forth hereinbefore. During this period, Water of condensation was continuously removed to avoid hydrolysis of the imidazolines. The amount of water removed over the entire reaction period corresponded with about 85 percent conversion of the carboxyl groups to imidazoline groups, leaving a balance of about 15 percent of the carboxyl groups in the form of amides. The composition of the reaction mixture was confirmed by infrared absorption analysis. Finally, the product was cooled under nitrogen to about 130 C.

The utility of the reaction product is demonstrated in the following Example 2:

Example 2 300 lbs. of a reaction product prepared according to the procedure of Example 1 were added to 300 lbs. of

epoxidized soybean oil and the mixture was heated for 1 hour at 130 C. with gentle stirring and then cooled.

quickline and 15 lbs. of polyethylene glycol 400 monooleate. (The numeral 400 designates the molecular weight of the polyethylene glycol moiety). The resulting composition was a thick, readily-flowable liquid and stable at room temperature. A portion of the printing plate composition was poured into an image-bearing mold adaptable for letterpress printing. The filled mold was then placed in a hydraulic press operating at a pressure of about 500 pounds per square inch over the peripheral edge of the mold and at a temperature of about 162.5 C. After a press molding period of about 5 minutes, the duplicate plate was stripped from the mold While hot without causing any distortion. Its flexible character Was such as to permit use on either rotary or flatbed presses. The raised images of the plate were sharp and gave a quality for reproducing fine detail and half-tone cuts comparable t electrotypes.

Eight 200-lb. batches of the triethylene tetramine-acids reaction product were prepared according to the procedure described in Example 1. The compositions of the resulting products as determined by infrared analysis were comprised of structures consisting of about 83-88 percent (average 85 percent) conversion of the carboxyl groups to imidazoline rings with the remaining 12-17 percent of the original carboxyl groups being converted to amide groups.

We claim:

1. A composition derived by reacting in a deoxygenated system 4 moles of oleic acid, 1 mole of a mixture of dimeric and trimeric fatty acids, 3 moles of sebacic acid and 8 moles of triethylene tetramine at a temperature of about C. to 240 C. and a pressure of about 10 to 760 mm. Hg while continuously removing the water of reaction, and continuing the reaction until the flow of Water of reaction substantially ceases, said dimeric-trimeric fatty acid mixture being a mixture of polymerized acids consisting of about percent dimeric and 25 percent trimeric acids derived from a mixture of unsaturated 18-carbon monocarboxylic acids.

2. A composition according to claim 1 wherein the reaction is carried out in the presence of a small amount of a chelating agent.

3. A composition according to claim 2 wherein the chelating agent is sodium tripolyphosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,374,354 Kaplan Apr. 24, 1945 2,568,876 White et al. Sept. 25, 1951 2,668,165 Carpenter Feb. 2, 1954 2,846,440 Hughes Aug. 5, 1958 2,917,376 Stromberg et a1. Dec. 15, 1959 

1. A COMPOSITION DERIVED BY REACTING IN A DEOXYGENATED SYSTEM 4 MOLES OF OLEIC ACID, 1 MOL OF A MIXTURE OF DIMERIC AND TRIMERIC FATTY ACIDS, 3 MOLES OF SEBACIC ACID AND 8 MOLES OF TRIETHYLENE TETRAMINE AT A TEMPERATURE OF ABOUT 50*C. TO 240*C. AND A PRESSURE OF ABOUT 10 TO 760MM. HG WHILE CONTINUOUSLY REMOVING THE WATER OF REACTION, AND CONTINUOUSLY THE REACTION UNTIL THE FLOW OF WATER OF REACTION SUBSTANTIALLY CEASES, SAID DIMERIC-TRIMERIC FATTY ACID MIXTURE BEING A MIXTURE OF POLYMERIZED ACIDS CONSISTING OF ABOUT 75 PERCENT DIMERIC AND 25 PERCENT TRIMERIC ACIDS DERIVED FROM A MIXTURE OF UNSATURATED 28-CARBON MONOCARBOXYLIC ACIDS. 